Diazotype photographic material



Patented Dec. 7, 1943 DIAZOTYPE rno'rocmmc MATERIAL John M. Snell, Waldemar Vanselow, and Arnold Weissberger, Rochester, N. Y Eastman Kodak Company, Rochester,

., assignors to N. Y., a

corporation of New Jersey No Drawing. Application May 29, 1941, Serial No. 395,822

6 Claims.

This invention relates to diazotype photographic materials. More particularly, it relates to diazotype copying materials wherein thellght sensitive compound is a diazo derivative of an arylamine having the general formula:

X B l group. More specifically, X can be hydrogen,

chlorine, bromine, methyl, ethyl, propyl, methoxy, ethoxy, acetamino, propionamino, sulphonic acid, and the like groups, R. can be methyl, ethyl, propyl, butyl, fl-methoxyethyl, hydroxyethyl, p -dihydrompropyl. and the like groups, and R1 can be carbamyl, methoxy, ethoxy, acetyl, carboxylic acid methyl ester, carboxylic acid ethyl ester, carborwlic acid propyl ester, methanesulfonamido, ethanesulfonamido, furyl, tetrahydrofuryl, and similar kind of groups.

We have found that the diazo derivatives of the above described substituted phenylene diamines are stable compounds under ordinary conditions, but decompose more or less completely on exposure to light. Since they are also capable of condensing with certain aromatic coupling compounds, as well as with their own partial decomposition products, in the presence of alkaline substances to form fast azo dyes, we have found further that our diam derivatives are valuable as light sensitive components in diazotype photographic copying materials. In the presence of selected coupling components on a suitable support, they produce on exposure to light behind a pattern such as a transparent photographic negative 'or positive, a line drawing, printed matter or other similar contrasty subject matter and subsequent alkaline processing, images having permanent dark lines and tones contrasted to almost white or slightly gray or tan fields. The prints are quite contrasty and show good keeping qualities. The alkaline processing consists ordinarily of subjecting the exposed diazotype sheet to an atmosphere of ammonia, but it is also possible to develop the image by means of a dilute aqueous solution of an alkylolamine such as triethanolamine or by means of steam in which case the sensitized coating must contain a suitable alkali incorporated therein. As will be more fully apparent from the examples given, we can prepare our new diazotype 'materials by a number of methods. For example, the base or support carrying or containing the light sensitive compounds can be paper, cloth or a film such as prepared rrom cellulose nitrate, cellulose acetate, cellulose acetatepropionate, regenerated cellulose, and the like, a glass plate or sheet metal, the sensitizing substance being applied by coating, dipping, brushing, spraying, dusting or by any other means known to one skilled in the art. are sensitizing compounds can be applied from a solution containing one or more of our diazo compounds together with one or more selected coupling components and may also have present one or more stabilizing compounds selected from the group including hydrochloric acid, boric acid, tartaric acid, thiourea, and the like. Ordinarily, however, the light sensitive compounds and the coupling compounds are dissolved in separate solutions and applied to the sheet material to be sensitized in sequence. The stabilizers are usually incorporated in the chemo salt solution.

After each .apphcatromtne sheet may be dried, if desired. Another modification is to add a thickening or emulsifying agent to the solution 'or solutions such as gelatin, polyvinyl alcohol, polyvinyl phthalate, cellulose acetate-phtnalate, gum tragacantn, a higher fatty acid glyceryl sulfate and similar kind of substances. The solution concentrations of the sensitizing compounds can be varied within fairly wide limits, the preferred range being up to about 2% by weight of the diazo compound, and about the same concentration, of the coupling compound. Good results have also been obtained with concentrations as high as 4% by weight of the respective components. The stabilizers can also :18 varied within fairly wide limits of concentra- It is an object of our invention, therefore, to provide diazotype photographic copying materials which combine the advantages of good stability, high degree of sensitivity to light, and produce prints which are characterized by excellent keeping qualities, good sharpness and contrast.

The substituted phenylene diamines of our invention can;be prepared by a number of methods. Onemethod is the react an ortho or para nitrochlorobenzene with the desired secondary aliphatic-amine, and then reduce with ammonium sulfide or with a nickel catalyst. In another method, N-ethyl-N-(4-amino-3- methylphenyl) glycineamide can be prepared by starting with N-ethyl-N-(3-methylphenyl) -glycineamide,,converting to the p-nitro derivative by nitration in the presence of sulphuric acid, isolating the product by crystallization, dissolving the crystals in ethanol and hydrogenating over nickel at temperatures of 50-150 0. and pressures up to 200 atmospheres. The amine canbe recovered by filtering out the nickel and concentrating the filtrate. Another method of preparing our substituted phenylene diamines is to startwith an N-alkyl-m-toluidine and condense it with an aliphatic halide of the type desired tobe introduced, treat the product with sodium nitrite and hydrochloric acid to convert to the nitroso derivative, and then reduce to the substituted phenylene diamine with zinc and hydrochloric acid- In the case of the furylamine intermediates employed in the above reactions, they can be prepared as described in McNally and Dickey, U. 8. Patent 2,191,030, issued Feb. 20, 1940, and Cliiford, U. s. Patent 2,173,711, issued Sept. 19, 1939. The N-hydroxyalkylphenylene diamines can be prepared by reacting phenylene diamine with analkyleneoxide as described in Wendt, U. S. Patent 2,108,243, issued Feb. 15,

The following examples further illustrate the preparation and application of: our=.new ,diazotype photographic printing and .copying materials.

Examp e Approximately 2 grams of N-ethyl-N-(4- amino-3-methylphenyl) -glycineamide HQNCOC was dissolved in 100 c. c. of water containinguf ficient mineral acid to maintain an acid condi: tion, ice added, and diazotized by the addition of a small excess of sodium nitrite. The diazonium compound obtained can be isolated as the zinc chloride" or cadmium chloride double salt, if desired, but usually the diazo solution can be used directly for sensitization without the necessity of isolating the diazonium compound. A piece of white paper was dipped in the diazo solution for a short period, the excess liquid drained of! or wiped 011, after which the paper was dipped in a 1% solution of p-naphthol in ethyl alcohol. After drying. the sensitized paper was exposed behind a positive to the radiation of a mercury vapor arc. The positive image I obtained at once on development in an atmosphere of ammonia, kept at slightly higher than room temperature, was dark purple in color on a white field. The stability of the unused, sensitized paper proved quite satisfactory when sub- Jected to a keeping test which consisted of heating the paper at 48 C. for a period of 5 days.

Example 2 A solution containing the diazonium compound of approximately 2 grams of N-ethyl-N-(4- amino-a-methylphenyl)-glycineamide, 4 grams of concentrated hydrochloric acid, 4 grams of boric acid, 8 grams of tartaric acid, 0.4 gram of thiourea and c. c. of water was applied to a piece of white paper. The excess liquid was removed and the paper then dipped in a 1% solution of p-naphthol in ethyl alcohol. After drying, the sensitized paper was exposed and developed as in Example 1. The print had a dark purple coloured image on a white field. The unused. sensitized paper showed good keeping qualities when treated at 48 C. for 5 days.

In place of N-ethyl-N-(4-amino-3-methylphe'nyD-glycineamide in the above example, there was substituted an equavilent amount of N-(p-methoxyethyl)-N-(4-amino- 3 -methylphenyl) glycineamide which produced a purple image on a white field, and N-methyl-N-paminophenyl-glycineamide which produced a red-brown image on a white field. The unused, sensitized papers in each case showed good keeping test results. a

Example 3 A solution made up similar to that of Example 2, but employing as the light sensitive material the diazonium compound of N-ethyl-N-(4- amino-3-methylphenyl) -glycine ethyl ester sulfate z The image of-theprint obtained was purple in color on a very pale tan field. The keeping test was satisfactory.

cgmococnf Example 5 A piece of white paper was sensitized, exposed and developed as described in Example 2, except the diazonium compound was a. derivative of 2- amino-5 (ethyl-p-methoxyethylamino)-toluene CHrO 021(4 $11 The image of the print obtained was dark purple in color on a white field. The keeping test was satisfactory.

Example 6 A piece of white paper was sensitized, exposed and developed as described in Example 2, except the diazonium compound was a derivative of 2- amino (p-hydroxyethyl tetrahydroiuriurylamino) -toluene 110- can N-QNH, t Jan-o4 Hi B c-CH;

tetrahydroturturylamino) -toluene which pro-' duced a purple colored image on a white field, N-ethyl-N-furiuryl-p-phenylene diamine which produced a dark brown colored image on an almost white field, and N-ethyl-N-tetrahydrofuriuryl-p-phenylene diamine which produced a red-brown colored image on a pale tan field. In each case, the unused, sensitized paper showed good keeping test results.

Example 7 A piece of white paper was sensitized, exposed and developed as described in Example 2, except the light sensitive compound was a diazo derivative of 2-amino-5-acetonyl ethylamino-toluene sulfate CSHJ CHaC OCH;

N HIJEhS O a The print obtained had a red-brown colored image on field of pale pink. The unused, sensitized paper showed a fair result on the keeping test.

In place of the 2-amino-5-acetonyl ethylamino-toluene sulfate in the above example, there was substituted 2-amino-5-ethyl-6-ketoamylamino-toluene sulfate, in which case there was obtained a print having a, dark purple colored image on a white field. The unused sensitized paper showed a good result on the keeping test. A corresponding print containing no stabilizers was almost as good in appearance, the image being dark purple in color on an almost white field.

While our invention has been illustrated more particularly in connection with fl-naphthol as the coupling component, it will be understood that other coupling components are likewise included within the scope of the invention. For example, in place of p-naphthol, there can be employed resorcinol, phloro-glucinol, 2,4-dichloro-1- naphthol, p-oxynaphthoic acid anilide, 4-benzoyll-naphthol, 2 chloro -1- naphthol, 4 chloro-1- naphthol, 2,4 dibromo-5-(N-benzyl-N-naphthalene-fi-sulfon) amido-I-naphthol, 2.4-dichloro-5- (N- benzyl-N-a-naphthoyl) amino 1 naphthol, 2,4-dichloro-5- (N-benzyl-N-p-naphthoyl) aminol-naphthol, methyl-l-naphthol-S-sulfonate, 5- [p- (p-acetaminobenzene sulfonamido) -benzamidoll-naphthol, 2-acety1-4-ch1oro-l-naphthol, 2- acetyl-l-naphthol, 4-acetyl-1-naphthol, 2-acetyll-naphthol-a-methyl-a-phenyl hydrazone, 2-acetyl-l-naphthol semlcarbazone, 5-(N-benzyl-N-namyl naphthalene-a (or p) -su1fon)amido-1-naphtho], 5- (N-benzyl-N-naphthalene-a-sulfon) amido-l-naphthol, 5-(N-benzyl-N-p-tert. amylbenzene-sulfon)amido-l-naphthol, S-(N-benzyl-N- n valeryl) amido -1- naphthol, 2-bromoacetyl-1- naphthol, Z-cinnamoyl-l-naphthol, 2,4-dichloro- 5 [p (p-benzamido) -benzamidol-1 naphthol, 2,4 dichloro 5 palmitylamino i-naphthol, 5-

(mm dinitrobenzoylamino) -1-naphthol, di piperldinomethyl-LS-dihydroxynaphthalene, l-hydroxy-2- (N-isoamyl-N-phenyl) -naphthamide, 1- hydroxy-2- (N-ethyl-N-a-naphthyl) naphthamide, 1-hydroxy-2-(N-methyl)-naphthanilide, 1- hydroxy-2-naphthanilide, 5-hydroxy-1-naphthoic acid, l-hydroxy-Z-naphthoic acid, 5-lauroylamino 1 naphthol, 4 methyl 1 -naphthol, 5- methyl sulfonylamino-l-naphthol, l-naphthol- 3,6 di(sulfon-N-methylanilide) 1 naphthol-4- sulfonanilide, 1-naphthol-4 sulf0n(N ethyl-anaphthalide) 5- (p-nitrobenzamido) -1-naphthol, 2-n-valery1-1-naphthol, 4-n-valeryl-1-naphthol, and the like. The methods 01 preparing the above mentioned a-naphthols are described in copending application Serial Number 361;263, now Patent No. 2,298,444.

While stabilizers have been illustrated-in the examples with the use of a mixture 01' hydrochloric acid, boric acid, tartaric acid and thiourea, it will be understood that the invention is not limited to this combination, since it is also possible to obtain excellently stabilized diazotype materials with any one or more or the above mentioned stabilizing compounds, as well as with other stabilizing compounds such as citric acid, lactic acid, sodium naphthalene-trisulfonate, oxalic acid, phosphoric acid, and similar kind of compounds.

We claim:

1. A diazotype photographic material comprising a light sensitive diazo derivative of a compound having the general formula:

N' NE:

wherein n represents a whole number not greater than 3, X represents a member selected from the group consisting of hydrogen, a halogen, an alkyl group, an alkoxy group, an acylamino group, and a sulphonic acid group, R represents a member selected from the group consisting of an alkyl group, a hydroxyalkyl group, and an alkoxyallwl group, and R1 represents a member selected from the group consisting of an alkoxy group, a fatty acid acyl group, a carboxylic acid alkyl ester group, an alkylsulionamido group, a furyl group, a carbamyl group, and a tetrahydrofuryl group.

2. A diazotype photographic material comprising a light sensitive diazo derivative 01' a compound having the general formula:

PN-Q-NH:

wherein n represents a whole number not greater than 3, X represents a member selected from the group consisting of hydrogen, a halogen, an alkyl group, an alkoxy group, an acylamino group, and a sulphonic acid group, and R represents a member selected from the group consisting of an alkyl group, a hydroxyalkyl group, and an alkoxyalkyl group.

3. A diazotype photographic material comprising a light sensitive diazo derivative of a compound having the general formula:

N I NH: 2) n wherein n represents a whole number not greater than 3, x represents a member selected from the group consisting of hydrogen, a halogen, an alkyl group. an alkoxy group, an acylamino group, and a sulphonic acid group, and R represents a member selected from the group consisting of an alkyl group, a hydroxyalkyl group, and an alkoxyallgvl group.

4. A diazotype photographic material comprising a light sensitive diazo derivative of a compound having the general formula:

CH C 0 (CH1) I l x wherein n represents a whole number not greater than 3, x represents a member selected from the group consisting of hydrogen, a halogen, an alkyl group, an alkoxy group, an acylamino group. and a sulphonic acid group, and R represents a member selected from the group consisting of an alkyl group, a hydroxyalkyl group, and an alkoxyalkyl group.

5. A diazotype photographic material comprising a light sensitive diazo derivative of a norm pound having the general formula:

CsHt

N NH:

mNc o 011/ JOHN M. SNEIL. WALDEIIAR VANSELOW. ARNOLD ER, 

